Pattern forming process and shrink agent

ABSTRACT

A negative pattern is formed by applying a resist composition onto a substrate, exposing the resist film, and developing the exposed resist film in an organic solvent developer. The process further involves coating the negative pattern with a shrink agent solution of a polymer comprising recurring units having an acid labile group-substituted hydroxyl and/or carboxyl group in a C 7 -C 16  ester or C 8 -C 16  ketone solvent, baking the coating, and removing the excessive shrink agent via organic solvent development for thereby shrinking the size of spaces in the pattern.

CROSS-REFERENCE TO RELATED APPLICATION

This non-provisional application claims priority under 35 U.S.C. §119(a)on Patent Application No. 2014-221355 filed in Japan on Oct. 30, 2014,the entire contents of which are hereby incorporated by reference.

TECHNICAL FIELD

This invention relates to a shrink agent and a pattern forming processcomprising forming a resist pattern via resist coating, exposure anddevelopment, coating the resist pattern with a shrink agent, baking, anddeveloping the shrink agent for shrinking the size of spaces in theresist pattern.

BACKGROUND ART

While the effort to reduce the pattern rule is in rapid progress to meetthe recent demand for higher integration level and operating speed ofLSIs, the photolithography is on widespread use. The photolithographyhas the essential limit of resolution determined by the wavelength of alight source. One micropatterning approach to go beyond the limit ofresolution is by combining ArF excimer laser immersion lithography withdouble patterning. One typical version of double patterning islitho-etch-litho-etch (LELE) process involving forming a pattern viaexposure, transferring the pattern to a hard mask on a substrate byetching, effecting second exposure at a half-pitch shifted position, andetching the hard mask. This process has the problem of misalignmentbetween two exposures or overlay error. Another version of doublepatterning is self-aligned double patterning (SADP) process involvingthe steps of transferring a resist pattern to a hard mask, growing afilm on opposite sides of hard mask features, and leaving sidewalls offilm for thereby doubling pattern size. The SADP process needs exposureonly once and mitigates the problem of overlay error. To simplify theprocess, a modified version of the SADP process of forming a siliconoxide film on sidewalls of resist pattern features as developed ratherthan sidewalls of hard mask features for thereby doubling pattern sizeis also proposed. Since the SADP process is successful in reducing thepitch of line pattern to half, the pitch can be reduced to ¼ byrepeating the SADP process twice.

Not only shrinking of line patterns, but also shrinking of hole patternsis necessary. Unless the hole pattern is shrunk, shrinkage over theentire chip is incomplete. One known method of shrinking a hole patternis RELACS® method described in JP-A H10-73927. This method intends toreduce the size of a hole pattern by coating a resist pattern asdeveloped with a water-soluble material containing a crosslinker, andbaking the coating to form a crosslinked layer on the resist surface forcausing the resist pattern to be thickened. JP-A 2008-275995 describes awater-soluble shrink material comprising an amino-containing polymer orpolyamine, which bonds to the resist surface via neutralization reactionwith carboxyl groups on the resist surface, for thereby thickening theresist film. It is also proposed in Proc. SPIE Vol. 8323 p 83230W-1(2012) to shrink a hole pattern by utilizing the direct self-assembly(DSA) of a block copolymer.

Shrinkage by the RELACS® method has the problem that since a crosslinkerbecomes active with an acid catalyst within resist, the size of holes isnon-uniform after shrinkage if acid diffusion is non-uniform. In theshrink method based on neutralization and bonding of water-soluble aminopolymer, the pattern is thickened as direct reflection of irregularitieson the resist surface so that dimensional variations of the resistpattern as developed and dimensional variations after shrinkage areidentical. The shrink method utilizing the DSA function of a blockcopolymer has advantages including an increased amount of shrinkage anda minimal dimensional variation after shrinkage, but some problems.Namely, if the DSA is applied to holes of different size, shrinkagecannot be induced for those holes of the size that causes acontradictory assembly of block copolymer. If the DSA is applied to atrench pattern, shape deformation becomes a problem, for example, aplurality of hole patterns are formed.

There is a need for a shrink agent which can shrink a trench patternwithout changing the shape of the resist pattern, and improve thedimensional variation and edge roughness (LWR) of the resist patternafter development.

CITATION LIST

-   Patent Document 1: JP-A H10-73927 (U.S. Pat. No. 6,579,657)-   Patent Document 2: JP-A 2008-275995 (US 20100119717)-   Non-Patent Document 1: Proc. SPIE Vol. 8323 p 83230W-1 (2012)

SUMMARY OF INVENTION

As discussed above, the method of applying a RELACS® material ofcrosslink type or neutralizing reaction-mediated bond type onto a resistpattern causes no pattern deformation, but fails to reduce thedimensional variation of the resist pattern. The DSA method can reducethe dimensional variation of a hole pattern as developed, but invitespattern deformation when applied to a trench pattern as developed.

An object of the invention is to provide a shrink agent which whencoated onto a resist pattern as developed, can reduce the dimensionalvariation of the resist pattern, and when applied to a trench pattern,can shrink the trench size without causing pattern deformation; and apattern forming process using the same.

In one aspect, the invention provides a pattern forming processcomprising the steps of:

applying a resist composition onto a substrate, the resist compositioncomprising a polymer comprising recurring units having an acid labilegroup-substituted carboxyl group, an acid generator and an organicsolvent,

prebaking to form a resist film,

exposing the resist film to high-energy radiation,

baking the film,

developing the exposed resist film in an organic solvent-based developerto form a negative pattern,

applying a shrink agent onto the negative pattern, the shrink agentbeing a solution of a polymer comprising recurring units having an acidlabile group-substituted hydroxyl and/or carboxyl group in a solventselected from the group consisting of ester solvents of 7 to 16 carbonatoms and ketone solvents of 8 to 16 carbon atoms,

baking, and

removing the excessive shrink agent with the organic solvent-baseddeveloper for thereby shrinking the size of spaces in the pattern.

In a preferred embodiment, the polymer in the shrink agent comprisesrecurring units having an acid labile group-substituted hydroxyl and/orcarboxyl group, represented by the general formula (1).

Herein R¹ and R³ each are hydrogen or methyl; R² and R⁵ each are an acidlabile group; X₁ is a single bond, a phenylene or naphthylene group, or—C(═O)—O—R⁶—, R⁶ is a straight, branched or cyclic C₁-C₁₀ alkylene groupwhich may contain ether, ester, lactone ring or hydroxyl, or a phenyleneor naphthylene group; X₂ is a single bond, a phenylene or naphthylenegroup which may contain nitro, cyano or halogen, or —C(═O)—O—R⁷—,—C(═O)—NH—R⁷—, —O—R⁷—, or —S—R⁷—, R⁷ is a straight, branched or cyclicC₁-C₁₀ alkylene group which may contain ether, ester, lactone ring orhydroxyl, or a phenylene or naphthylene group which may contain astraight, branched or cyclic C₁-C₆ alkyl, alkoxy, acyl, acyloxy, C₂-C₆alkenyl, alkoxycarbonyl, C₆-C₁₀ aryl, nitro, cyano, or halogen; R⁴ is asingle bond, a di to penta-valent, straight, branched or cyclic C₁-C₁₆aliphatic hydrocarbon group, or phenylene group, which may contain etheror ester; 0≦a1≦1.0, 0≦a2<1.0, 0<a1+a2≦1.0, and n is 1 to 4.

More preferably, the polymer comprising recurring units having an acidlabile group-substituted hydroxyl and/or carboxyl group, represented byformula (1) further comprises recurring units (b) having a hydroxyl,carboxyl, lactone ring, lactam ring, sultone ring, sulfone, sulfonicacid ester, sulfonamide, carboxylic amide, nitro, cyano, thienyl, furyl,pyrrole, acid anhydride, imide, —NH—(C═O)—O—, —S—(C═O)—O, or —ON(═O₂)—,recurring units (d) having an oxirane or oxetane ring, and/or recurringunits (e) having an amino group.

In a preferred embodiment, the solvent in the shrink agent is at leastone solvent selected from ester solvents of 7 to 16 carbon atomsincluding amyl acetate, isoamyl acetate, 2-methylbutyl acetate, hexylacetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexylacetate, hexyl formate, ethyl valerate, propyl valerate, isopropylvalerate, butyl valerate, isobutyl valerate, tert-butyl valerate, amylvalerate, isoamyl valerate, ethyl isovalerate, propyl isovalerate,isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate,tert-butyl isovalerate, isoamyl isovalerate, ethyl 2-methylvalerate,butyl 2-methylvalerate, ethyl pivalate, propyl pivalate, isopropylpivalate, butyl pivalate, tert-butyl pivalate, ethyl pentenoate, propylpentenoate, isopropyl pentenoate, butyl pentenoate, tert-butylpentenoate, propyl crotonate, isopropyl crotonate, butyl crotonate,tert-butyl crotonate, butyl propionate, isobutyl propionate, tert-butylpropionate, benzyl propionate, ethyl hexanoate, allyl hexanoate, propylbutyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate,tert-butyl butyrate, ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate,methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenylacetate, benzyl acetate, methyl phenylacetate, benzyl formate,phenylethyl formate, methyl 3-phenylpropionate, ethyl phenylacetate, and2-phenylethyl acetate, and ketone solvents of 8 to 16 carbon atomsincluding 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone,4-nonanone, 5-nonanone, ethylcyclohexanone, ethylacetophenone, ethyln-butyl ketone, di-n-butyl ketone, and diisobutyl ketone.

In a preferred embodiment, the shrink agent further comprises a saltcompound having the general formula (3)-1 or (3)-2 defined below.

In a preferred embodiment, the polymer in the resist compositioncomprises recurring units (a3) having the general formula (2):

wherein R⁸ is hydrogen or methyl, R⁹ is an acid labile group, Z is asingle bond or —C(═O)—O—R¹⁰—, R¹⁰ is a straight, branched or cyclicC₁-C₁₀ alkylene group which may contain ether or ester, or naphthylenegroup, and 0<a3<1.0.

In a preferred embodiment, the developer comprises at least one organicsolvent selected from the group consisting of 2-octanone, 2-nonanone,2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone,diisobutyl ketone, methylcyclohexanone, acetophenone,methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate,amyl acetate, isoamyl acetate, butenyl acetate, propyl formate, butylformate, isobutyl formate, amyl formate, isoamyl formate, methylvalerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methylpropionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate,ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyllactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate,benzyl acetate, methyl phenylacetate, benzyl formate, phenylethylformate, methyl 3-phenylpropionate, benzyl propionate, ethylphenylacetate, and 2-phenylethyl acetate.

Typically, the high-energy radiation in the exposure step is i-line ofwavelength 364 nm, KrF excimer laser of wavelength 248 nm, ArF excimerlaser of wavelength 193 nm, EUV of wavelength 13.5 nm, or EB.

In another aspect, the invention provides a shrink agent comprising apolymer comprising recurring units having an acid labilegroup-substituted hydroxyl and/or carboxyl group, an ester solvent of 7to 16 carbon atoms and/or ketone solvent of 8 to 16 carbon atoms, and asalt compound having the general formula (3)-1 or (3)-2:

R¹¹—CO₂ ⁻M⁺  (3)-1

R¹²—SO₃ ⁻M⁺  (3)-2

wherein R¹¹ and R¹² each are a straight, branched or cyclic C₁-C₂₀ alkylgroup, C₂-C₂₀ alkenyl group or C₆-C₂₀ aryl group which may containfluorine, ether, ester, lactone ring, lactam ring, carbonyl or hydroxyl,and M is sulfonium, iodonium or ammonium.

Advantageous Effects of Invention

The process of the invention involves forming a resist film of aphotoresist composition comprising a polymer having an acid labilegroup-substituted carboxyl group and an acid generator, forming anegative tone pattern from the resist film via exposure and organicsolvent development, coating the resist pattern with a shrink agent,i.e., a solution of a polymer comprising recurring units having an acidlabile group-substituted carboxyl and/or hydroxyl group in an estersolvent of 7 to 16 carbon atoms or ketone solvent of 8 to 16 carbonatoms which does not dissolve the resist pattern, baking, and removingthe excessive shrink agent via organic solvent development again. Thesize of spaces in the resist pattern can be shrunk in a preciselysize-controlled manner.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1A-1C illustrate, in cross-sectional views, early steps of apattern forming or shrinking process according to the invention; FIG. 1(A) showing a photoresist film formed on a substrate; FIG. 1 (B) showingthe photoresist film during exposure; and FIG. 1 (C) showing patternformation after PEB and development of the photoresist film.

FIGS. 2D-2F illustrate, in cross-sectional views, later steps of thepattern forming or shrinking process according to the invention; FIG. 2(D) showing a shrink agent coated on the resist pattern; FIG. 2 (E)showing the resist pattern whose spaces have been shrunk by baking andremoval of the excessive shrink agent; and FIG. 2 (F) showing dryetching of the substrate through the shrunk space pattern as a mask.

DESCRIPTION OF PREFERRED EMBODIMENTS

The terms “a” and “an” herein do not denote a limitation of quantity,but rather denote the presence of at least one of the referenced item.“Optional” or “optionally” means that the subsequently described eventor circumstances may or may not occur, and that description includesinstances where the event or circumstance occurs and instances where itdoes not. As used herein, the notation (C_(n)-C_(m)) means a groupcontaining from n to m carbon atoms per group. As used herein, the term“film” is used interchangeably with “coating” or “layer.”

The abbreviations and acronyms have the following meaning.

Mw: weight average molecular weight

Mn: number average molecular weight

Mw/Mn: molecular weight distribution or dispersity

GPC: gel permeation chromatography

PEB: post-exposure bake

PAG: photoacid generator

LWR: line width roughness

LER: line edge roughness

Searching for a shrink material capable of effectively shrinking aresist pattern as developed and a shrink process using the same, theinventors have found the following. A photoresist composition comprisinga polymer having an acid labile group-substituted carboxyl group and anacid generator is coated to form a resist film. The resist film isprocessed via exposure and organic solvent development to form anegative tone resist pattern. Thereafter, the size of spaces in theresist pattern can be shrunk in a precisely size-controlled manner bycoating the resist pattern with a shrink agent, i.e., a solution of apolymer comprising recurring units having an acid labilegroup-substituted carboxyl and/or hydroxyl group in an ester solvent of7 to 16 carbon atoms or ketone solvent of 8 to 16 carbon atoms, baking,and removing the excessive shrink agent via organic solvent development.

The shrink agent used in the pattern forming process of the invention isa solution of a polymer in a solvent. The polymer is defined ascomprising recurring units having an acid labile group-substitutedhydroxyl and/or carboxyl group, preferably represented by the generalformula (1).

Herein R¹ and R³ each are hydrogen or methyl. R² and R⁵ each are an acidlabile group. X₁ is a single bond, a phenylene or naphthylene group, or—C(═O)—O—R⁶—, wherein R⁶ is a straight, branched or cyclic C₁-C₁₀alkylene group which may contain an ether moiety, ester moiety, lactonering or hydroxyl moiety, or a phenylene or naphthylene group. X₂ is asingle bond, a phenylene or naphthylene group which may contain nitro,cyano or halogen, or —C(═O)—O—R⁵—, —C(═O)—NH—R⁷—, —O—R⁷—, or —S—R⁷—,wherein R⁷ is a straight, branched or cyclic C₁-C₁₀ alkylene group whichmay contain an ether moiety, ester moiety, lactone ring or hydroxylmoiety, or a phenylene or naphthylene group which may contain astraight, branched or cyclic C₁-C₆ alkyl, alkoxy, acyl, acyloxy, C₂-C₆alkenyl, alkoxycarbonyl, C₆-C₁₀ aryl, nitro, cyano, or halogen. R⁴ is asingle bond, a di to penta-valent, straight, branched or cyclic C₁-C₁₆aliphatic hydrocarbon group, or phenylene group, which may contain anether or ester moiety. The subscripts a1 and a2 are numbers in therange: 0≦a1≦1.0, 0≦a2<1.0, 0<a1+a2≦1.0, and n is 1 to 4.

It should be avoided that when the shrink agent solution is applied ontoa resist pattern, the resist pattern is dissolved in the solvent of theshrink agent. To this end, the solvent of the shrink agent must beselected from those solvents that do not dissolve the resist film. Thesolvents that do not dissolve the resist film include ether solvents of6 to 12 carbon atoms, alcohol solvents of 4 to 10 carbon atoms,hydrocarbon solvents of 6 to 12 carbon atoms, ester solvents of 7 to 16carbon atoms, ketone solvents of 8 to 16 carbon atoms, and water.Although a number of water-based shrink agents are already proposed asalluded to previously, they are difficult to quickly apply tolarge-diameter wafers because of the high surface tension of water. Aproblem arises particularly in the case of a fine hole pattern formedvia negative development. When holes are filled with the shrink agent byspin coating, the water solvent having a high surface tension preventsthe shrink agent from burying in the holes to the bottom. In contrast,when a shrink agent dissolved in an organic solvent having a lowersurface tension than water is applied, the ability to fill or bury tothe hole bottom is improved. Also the organic solvent used in the shrinkagent must dissolve the base polymer of the shrink agent. As the solventcapable of dissolving a polymer comprising recurring units having anacid labile group-substituted carboxyl and/or hydroxyl group, estersolvents of 7 to 16 carbon atoms and ketone solvents of 8 to 16 carbonatoms must be selected among the aforementioned organic solvents.

Monomers Ma1 and Ma2 from which recurring units (a1) and (a2) arederived have the following formulae.

Herein R¹ to R⁵, X₁, X₂, and n are as defined above.

Examples of monomer Ma1 wherein X₁ is a variant are shown below. HereinR¹ and R² are as defined above.

Examples of monomer Ma2 wherein X₂ and R⁴ are variants are shown below.Herein R³ and R⁵ are as defined above.

In addition to recurring units (a1) and/or (a2), the polymer for theshrink agent may further comprise recurring units (b) having a hydroxyl,carboxyl, lactone ring, lactam ring, sultone ring, sulfone, sulfonicacid ester, sulfonamide, carboxylic acid amide, nitro, cyano, thienyl,furyl, pyrrole, acid anhydride, imide, —NH—(C═O)—O—, —S—(C═O)—O, or—ON(═O₂)—. Examples of the monomer from which recurring units (b) arederived are shown below.

In the polymer comprising the aforementioned recurring units (a1), (a2)and (b), additional recurring units may be copolymerized. Exemplary arerecurring units (c) having a non-leaving hydrocarbon group as describedin JP-A 2008-281980. Suitable non-leaving hydrocarbon groups includethose described in JP-A 2008-281980, and indenes, acenaphthylenes, andnorbornadienes. By copolymerizing recurring units (c) having anon-leaving hydrocarbon group, the polymer is improved in solubility inthe C₇-C₁₆ ester and C₈-C₁₆ ketone solvents, and also improved in dryetching resistance when the substrate is etched through the patternafter shrinkage.

Further, recurring units (d) having an oxirane or oxetane ring may becopolymerized. Once recurring units (d) having an oxirane or oxetanering are copolymerized, crosslinking can take place at the interfacebetween the shrink agent and the resist film, leading to an increase ofshrinkage. Examples of the monomers from which recurring units (d)having an oxirane or oxetane ring are derived are shown below. Note thatR⁴¹ is hydrogen or methyl.

Still further, recurring units (e) having an amino group may becopolymerized. The recurring units (e) having an amino group may havethe general formula (4).

Herein R⁴² is hydrogen or methyl. X₃ is a single bond, phenylene groupor —C(═O)—O—. R⁴³ is a single bond, a straight, branched or cyclicC₁-C₁₀ alkylene group which may contain an ether moiety, ester moiety,—N═ or —S—, or a phenylene or naphthylene group. R⁴⁴ and R⁴⁵ each are astraight or branched C₁-C₄ alkyl group, R⁴⁴ and R⁴⁵ may bond together toform a ring which may contain an ether bond, or either one of R⁴⁴ andR⁴⁵ may bond with R⁴³ to form a ring; m is 1 or 2, and e is a number of0≦e≦0.8.

Examples of the monomer from which recurring units (e) having an aminogroup are derived are shown below. R⁴², R⁴⁴ and R⁴⁵ are as definedabove.

The acid labile group R² substituting on the carboxyl group and the acidlabile group R⁵ substituting on the hydroxyl group in the base polymerof formula (1) for the shrink agent, and the acid labile group R⁹substituting on the carboxyl group in the base polymer of formula (2)for the photoresist (to be described later) may be selected from avariety of such groups while they may be the same or different.Preferred acid labile groups include groups of formula (AL-10), acetalgroups of formula (AL-11), tertiary alkyl groups of formula (AL-12), andoxoalkyl groups of 4 to 20 carbon atoms.

In formulae (AL-10) and (AL-11), R⁵¹ and R⁵⁴ each are a monovalenthydrocarbon group, typically a straight, branched or cyclic alkyl groupof 1 to 40 carbon atoms, more specifically 1 to 20 carbon atoms, whichmay contain a heteroatom such as oxygen, sulfur, nitrogen or fluorine.The subscript “a5” is an integer of 0 to 10, preferably 1 to 5. R⁵² andR⁵³ each are hydrogen or a monovalent hydrocarbon group, typically astraight, branched or cyclic C₁-C₂₀ alkyl group, which may contain aheteroatom such as oxygen, sulfur, nitrogen or fluorine. Alternatively,a pair of R⁵² and R⁵³, R⁵² and R⁵⁴, or R⁵³ and R⁵⁴, taken together, mayform a ring, specifically aliphatic ring, with the carbon atom or thecarbon and oxygen atoms to which they are attached, the ring having 3 to20 carbon atoms, especially 4 to 16 carbon atoms.

In formula (AL-12), R⁵⁵, R⁵⁶ and R⁵⁷ each are a monovalent hydrocarbongroup, typically a straight, branched or cyclic C₁-C₂₀ alkyl group,which may contain a heteroatom such as oxygen, sulfur, nitrogen orfluorine. Alternatively, a pair of R⁵⁵ and R⁵⁶, R⁵⁵ and R⁵⁷, or R⁵⁶ andR⁵⁷, taken together, may form a ring, specifically aliphatic ring, withthe carbon atom to which they are attached, the ring having 3 to 20carbon atoms, especially 4 to 16 carbon atoms.

Illustrative examples of the groups of formula (AL-10) includetert-butoxycarbonyl, tert-butoxycarbonylmethyl, tert-amyloxycarbonyl,tert-amyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl,2-tetrahydropyranyloxycarbonylmethyl and2-tetrahydrofuranyloxycarbonylmethyl as well as substituent groups ofthe following formulae (AL-10)-1 to (AL-10)-10.

In formulae (AL-10)-1 to (AL-10)-10, R⁵⁸ is independently a straight,branched or cyclic C₁-C₈ alkyl group, C₆-C₂₀ aryl group or C₇-C₂₀aralkyl group; R⁵⁹ is hydrogen or a straight, branched or cyclic C₁-C₂₀alkyl group; R⁶⁰ is a C₆-C₂₀ aryl group or C₇-C₂₀ aralkyl group; and“a5” is an integer of 0 to 10 as defined above.

Illustrative examples of the acetal group of formula (AL-11) includethose of the following formulae (AL-11)-1 to (AL-11)-112.

The polymer may be crosslinked within the molecule or between moleculeswith acid labile groups of formula (AL-11a) or (AL-11b).

Herein R⁶¹ and R⁶² each are hydrogen or a straight, branched or cyclicC₁-C₈ alkyl group, or R⁶¹ and R⁶², taken together, may form a ring withthe carbon atom to which they are attached, and R⁶¹ and R⁶² are straightor branched C₁-C₈ alkylene groups when they form a ring. R⁶³ is astraight, branched or cyclic C₁-C₁₀ alkylene group. Each of b5 and d5 is0 or an integer of 1 to 10, preferably 0 or an integer of 1 to 5, and c5is an integer of 1 to 7. “A” is a (c5+1)-valent aliphatic or alicyclicsaturated hydrocarbon group, aromatic hydrocarbon group or heterocyclicgroup having 1 to 50 carbon atoms, which may be separated by aheteroatom such as oxygen, sulfur or nitrogen or in which some of thehydrogen atoms attached to carbon atoms may be substituted by hydroxyl,carboxyl, carbonyl radicals or fluorine atoms. “B” is —CO—O—, —NHCO—O—or —NHCONH—.

Preferably, “A” is selected from divalent to tetravalent, straight,branched or cyclic C₁-C₂₀ alkylene, alkanetriyl and alkanetetraylgroups, and C₆-C₃₀ arylene groups, which may be separated by aheteroatom such as oxygen, sulfur or nitrogen or in which some of thehydrogen atoms attached to carbon atoms may be substituted by hydroxyl,carboxyl, acyl radicals or halogen atoms. The subscript c5 is preferablyan integer of 1 to 3.

The crosslinking acetal groups of formulae (AL-11a) and (AL-11b) areexemplified by the following formulae (AL-11)-113 through (AL-11)-120.

Illustrative examples of the tertiary alkyl of formula (AL-12) includetert-butyl, triethylcarbyl, 1-ethylnorbornyl, 1-methylcyclohexyl,1-ethylcyclopentyl, and tert-amyl groups as well as those of (AL-12)-1to (AL-12)-16.

Herein R⁶⁴ is independently a straight, branched or cyclic C₁-C₈ alkyl,C₆-C₂₀ aryl or C₇-C₂₀ aralkyl group, or two R⁶⁴ may bond together toform a ring. R⁶⁵ and R⁶⁷ each are hydrogen, methyl or ethyl. R⁶⁶ is aC₆-C₂₀ aryl or C₇-C₂₀ aralkyl group.

Also included are acid labile groups of the formula (AL-12)-17.

Herein R⁶⁴ is as defined above, R⁶⁸ is a single bond or a straight,branched or cyclic C₁-C₂₀ alkylene group or arylene group which maycontain a heteroatom such as oxygen, sulfur or nitrogen, and b6 is aninteger of 0 to 3. With acid labile groups of formula (AL-12)-17containing R⁶⁸ representative of a di- or poly-valent alkylene orarylene group, the polymer may be crosslinked within the molecule orbetween molecules. It is noted that formula (AL-12)-17 is applicable toall the foregoing acid labile groups R², R⁵ and W.

The groups represented by R⁶⁴, R⁶⁵, R⁶⁶ and R⁶⁷ may contain a heteroatomsuch as oxygen, nitrogen or sulfur. Such groups are exemplified by thoseof the following formulae (AL-13)-1 to (AL-13)-7.

Of the acid labile groups of formula (AL-12), groups of exo-formstructure having the following formula (AL-12)-19 are preferred.

Herein R⁶⁹ is a straight, branched or cyclic C₁-C₈ alkyl group oroptionally substituted C₆-C₂₀ aryl group. R⁷⁰ to R⁷⁵, R⁷⁸, and R⁷⁹ areeach independently hydrogen or a monovalent C₁-C₁₅ hydrocarbon group,typically alkyl, which may contain a heteroatom, R⁷⁶ and R⁷⁷ arehydrogen; or a pair of R⁷⁰ and R⁷¹, R⁷² and R⁷⁴, R⁷² and R⁷⁵, R⁷³ andR⁷⁵, R⁷³ and R⁷⁹, R⁷⁴ and R⁷⁸, R⁷⁶ and R⁷⁷, or R⁷⁷ and R⁷⁸ may bondtogether to form a ring, typically aliphatic ring, with the carbon atomto which they are attached, and in this case, the ring-formingparticipant is a divalent C₁-C₁₅ hydrocarbon group, typically alkylene,which may contain a heteroatom. Also, a pair of R⁷⁰ and R⁷⁹, R⁷⁶ andR⁷⁹, or R⁷² and R⁷⁴ which are attached to vicinal carbon atoms may bondtogether directly to form a double bond. The formula also represents anenantiomer.

The ester form monomers from which recurring units having an exo-formstructure represented by the formula (AL-12)-19 shown below are derivedare described in U.S. Pat. No. 6,448,420 (JP-A 2000-327633).

R¹ is as defined above. Illustrative non-limiting examples of suitablemonomers are given below.

Also included in the acid labile groups of formula (AL-12) are acidlabile groups having furandiyl, tetrahydrofurandiyl or oxanorbornanediylas represented by the following formula (AL-12)-20.

Herein, R⁸⁰ and R⁸¹ are each independently a monovalent hydrocarbongroup, typically a straight, branched or cyclic C₁-C₁₀ alkyl group. R⁸⁰and R⁸¹, taken together, may form an aliphatic hydrocarbon ring of 3 to20 carbon atoms with the carbon atom to which they are attached. R⁸² isa divalent group selected from furandiyl, tetrahydrofurandiyl andoxanorbornanediyl. R⁸³ is hydrogen or a monovalent hydrocarbon group,typically a straight, branched or cyclic C₁-C₁₀ alkyl group, which maycontain a heteroatom.

Recurring units substituted with an acid labile group having furandiyl,tetrahydrofurandiyl or oxanorbornanediyl as represented by the formula:

(wherein R¹, R⁸⁰ to R⁸³ are as defined above) are derived from monomers,examples of which are shown below. Note that Me is methyl and Ac isacetyl.

Of the acid labile groups of tertiary alkyl form having formula (AL-12),those acid labile groups having a branched alkyl directly attached tothe ring offer high solubility in organic solvents. Such acid labilegroups are exemplified below. In the following formula, the line segmentprotruding out of the bracket denotes a valence bond.

In the polymer for the shrink agent, the recurring units (a1), (a2),(b), (c), (d) and (e) are present in proportions a1, a2, b, c, d, and e,respectively, which satisfy the range: 0≦a1≦1.0, 0≦a2<1.0, 0<a1+a2≦1.0,0≦b≦0.9, 0≦c≦0.8, 0≦d≦0.8, and 0≦e≦0.8; preferably 0≦a1≦0.9, 0≦a2≦0.9,0.1≦a1+a2≦0.9, 0.1≦b≦0.9, 0≦c≦0.7, 0≦d≦0.7, and 0≦e≦0.7; and morepreferably 0≦a1≦0.85, 0≦a2≦0.85, 0.2≦a1+a2≦0.85, 0.15≦b≦0.8, 0≦c≦0.6,0≦d≦0.6, and 0≦e≦0.6; provided that a1+a2+b+c+d+e=1.

On the other hand, the base resin in the resist composition used to forma resist pattern is a polymer comprising recurring units (a3) having anacid labile group-substituted carboxyl group, preferably represented bythe general formula (2).

Herein R⁸ is hydrogen or methyl. R⁹ is an acid labile group. Z is asingle bond or —C(═O)—O—R¹⁰— wherein R¹⁰ is a straight, branched orcyclic C₁-C₁₀ alkylene group which may contain an ether or ester moiety,or naphthylene group, and a3 is a number in the range: 0<a3<1.0.

In the polymer comprising recurring units (a3) for use in the resistcomposition, recurring units (b) as described above may be copolymerizedfor improving the insolubility of the exposed region in organic solventdeveloper, improving adhesion to the substrate, and preventing patterncollapse. Further, there may be copolymerized recurring units having anadhesive group selected from among hydroxyl, lactone ring, ether, ester,carbonyl and cyano groups as described in JP-A 2012-37867, paragraphs[0076]-[0084], an indene, acenaphthylene, chromone, coumarin, andnorbornadiene as described in paragraph [0085], a styrene,vinylnaphthalene, vinylanthracene, vinylpyrene, and methyleneindane asdescribed in paragraph [0088], and an acid generator in the form of anonium salt having polymerizable olefin as described in paragraphs[0089]-[0091].

The following discussion applies to both the polymer serving as theshrink agent and the polymer serving as the base resin in the resistcomposition, both used in the patterning process. The polymer shouldpreferably have a weight average molecular weight (Mw) in the range of1,000 to 500,000, and more preferably 2,000 to 100,000, as measured byGPC versus polystyrene standards. If Mw is too low, in the case ofshrink agent, the amount of shrinkage may become excessive or evenuncontrollable due to an extended acid diffusion distance, and in thecase of resist composition, the diffusion distance of acid generated byPAG may be extended to invite a drop of resolution. If Mw is too high,in the case of shrink agent, the solubility of the polymer in strippersolvent may be reduced, leaving scum in spaces at the end of removalstep, and in the case of resist composition, a footing phenomenon islikely to occur after pattern formation.

If a polymer has a wide molecular weight distribution or dispersity(Mw/Mn), which indicates the presence of lower and higher molecularweight polymer fractions, there is a possibility that foreign matter isleft on the pattern or the pattern profile is degraded. The influencesof molecular weight and dispersity become stronger as the pattern rulebecomes finer. Therefore, the multi-component copolymer shouldpreferably have a narrow dispersity (Mw/Mn) of 1.0 to 2.0, especially1.0 to 1.5, in order to provide a resist composition suitable formicropatterning to a small feature size.

It is understood that a blend of two or more polymers which differ incompositional ratio, molecular weight or dispersity is acceptable.

The polymers used herein may be synthesized by any desired method, forexample, by dissolving one or more monomers in an organic solvent,adding a radical initiator thereto, and effecting heat polymerization.The monomers used herein include monomers corresponding to recurringunits (a1), (a2), (b), (c), (d) and (e) in the case of shrink agentpolymer, and monomers corresponding to acid labile group-bearingrecurring units (a3), adhesive group-bearing recurring units (b) and thelike in the case of resist polymer, and other unsaturated bond-bearingmonomers. Examples of the organic solvent which can be used forpolymerization include toluene, benzene, tetrahydrofuran, diethyl etherand dioxane. Examples of the polymerization initiator used hereininclude 2,2′-azobisisobutyronitrile (AIBN),2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide.Preferably the system is heated at 50 to 80° C. for polymerization totake place. The reaction time is 2 to 100 hours, preferably 5 to 20hours. The acid labile group that has been incorporated in the monomermay be kept as such, or the acid labile group may be once removed withan acid catalyst and the resulting polymer be protected or partiallyprotected. In the polymer serving as the shrink agent, recurring units(a1), (a2) and (b) may be arranged randomly or blockwise.

The shrink agent used in the pattern forming process further contains anorganic solvent and optionally a salt, basic compound and surfactant.

It is essential that the organic solvent do not dissolve the resist filmafter development. The organic solvent is selected from ester solventsof 7 to 16 carbon atoms and ketone solvents of 8 to 16 carbon atoms.Suitable ester solvents include amyl acetate, isoamyl acetate,2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate, cyclohexylacetate, methylcyclohexyl acetate, hexyl formate, ethyl valerate, propylvalerate, isopropyl valerate, butyl valerate, isobutyl valerate,tert-butyl valerate, amyl valerate, isoamyl valerate, ethyl isovalerate,propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutylisovalerate, tert-butyl isovalerate, isoamyl isovalerate, ethyl2-methylvalerate, butyl 2-methylvalerate, ethyl pivalate, propylpivalate, isopropyl pivalate, butyl pivalate, tert-butyl pivalate, ethylpentenoate, propyl pentenoate, isopropyl pentenoate, butyl pentenoate,tert-butyl pentenoate, propyl crotonate, isopropyl crotonate, butylcrotonate, tert-butyl crotonate, butyl propionate, isobutyl propionate,tert-butyl propionate, benzyl propionate, ethyl hexanoate, allylhexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate,3-methylbutyl butyrate, tert-butyl butyrate, ethyl 2-methylbutyrate,isopropyl 2-methylbutyrate, methyl benzoate, ethyl benzoate, propylbenzoate, butyl benzoate, phenyl acetate, benzyl acetate, methylphenylacetate, benzyl formate, phenylethyl formate, methyl3-phenylpropionate, ethyl phenylacetate, and 2-phenylethyl acetate.Suitable ketone solvents include 2-octanone, 3-octanone, 4-octanone,2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, ethylcyclohexanone,ethylacetophenone, ethyl n-butyl ketone, di-n-butyl ketone, anddiisobutyl ketone. These solvents may be used alone or in admixture oftwo or more.

For the purpose of preventing intermixing of the shrink agent and theresist pattern, any of C₃-C₁₀ alcohol, C₈-C₁₂ ether, C₆-C₁₂ alkane,alkene, alkyne and aromatic solvents may be blended with the abovesolvent. Specifically, suitable alkanes of 6 to 12 carbon atoms includehexane, heptane, octane, nonane, decane, undecane, dodecane,methylcyclopentane, dimethylcyclopentane, cyclohexane,methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, andcyclononane. Suitable alkenes of 6 to 12 carbon atoms include hexene,heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene,cycloheptene, and cyclooctene. Suitable alkynes of 6 to 12 carbon atomsinclude hexyne, heptyne, and octyne. Suitable alcohols of 3 to 10 carbonatoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol,2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol,2-pentanol, 3-pentanol, tert-amyl alcohol, neopentyl alcohol,2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol,cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol,3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol,2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol,3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol,4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol,cyclohexanol, and 1-octanol. Suitable ether compounds of 8 to 12 carbonatoms include di-n-butyl ether, diisobutyl ether, di-sec-butyl ether,di-n-pentyl ether, diisopentyl ether, di-sec-pentyl ether, di-tert-amylether, and di-n-hexyl ether. Suitable aromatic solvents include toluene,xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, mesitylene,and anisole. The solvents may be used alone or in admixture.

In the shrink agent solution, the solvent is preferably used in anamount of 100 to 100,000 parts, more preferably 200 to 50,000 parts byweight per 100 parts by weight of the polymer.

To the shrink agent, a salt and basic compound may be added if desired.The salt that can be added is typically selected from sulfonium saltsand iodonium salts which are typically added to resist compositions, andammonium salts. The basic compound that can be added may be selectedfrom those basic compounds which are typically added to resistcompositions, for example, primary, secondary and tertiary aliphaticamines, mixed amines, aromatic amines, heterocyclic amines,nitrogen-containing compounds having carboxyl group, nitrogen-containingcompounds having sulfonyl group, nitrogen-containing compounds havinghydroxyl group, nitrogen-containing compounds having hydroxyphenylgroup, alcoholic nitrogen-containing compounds, amide derivatives, andimide derivatives. The addition of the salt or basic compound iseffective for suppressing excessive diffusion of acid from within theresist film and for controlling the amount of shrinkage. The surfactantthat can be added may be selected from those surfactants which aretypically added to resist compositions.

As the salt, a salt compound having the general formula (3)-1 or (3)-2is preferred.

R¹¹—CO₂ ⁻M⁺  (3)-1

R¹²—SO₃ ⁻M⁺  (3)-2

Herein R¹¹ and R¹² each are a straight, branched or cyclic C₁-C₂₀ alkylgroup, C₂-C₂₀ alkenyl group or C₆-C₂₀ aryl group which may containfluorine, ether moiety, ester moiety, lactone ring, lactam ring,carbonyl moiety or hydroxyl moiety, and M is sulfonium, iodonium orammonium.

Examples of the anion: R¹¹—CO₂ ⁻ are shown below.

Examples of the anion: R¹²—SO₃ ⁻ are shown below.

Of the salt compounds of formula (3)-1, sulfonium, iodonium and ammoniumsalts of carboxylic acid represented by formulae (P1a-1) to (P1a-3) arepreferred. Of the salt compounds of formula (3)-2, sulfonium, iodoniumand ammonium salts of sulfonic acid represented by formulae (P1b-1) to(P1b-3) are preferred. Acid diffusion may be effectively controlled byadding these salts.

Herein R^(101a), R^(101b), R^(101c) and R^(101d) are each independentlystraight, branched or cyclic C₁-C₁₂ alkyl, alkenyl, oxoalkyl oroxoalkenyl, C₆-C₂₀ aryl, or C₇-C₁₂ aralkyl or aryloxoalkyl group, inwhich some or all hydrogen atoms may be replaced by alkoxy or othergroups, R^(101b) and R^(101c) may bond together to form a ring which maycontain an ether, ester, sultone or amino moiety, each of R^(101b) andR^(101c) is C₁-C₁₀alkylene or arylene when they form a ring. R¹¹ and R¹²are as defined above.

In the shrink agent, preferably the salt is used in an amount of 0 to 50parts by weight, the basic compound is used in an amount of 0 to 30parts by weight, and the surfactant is used in an amount of 0 to 10parts, more preferably 0 to 5 parts by weight, all per 100 parts byweight of the polymer. When added, each additive is preferably used inan amount of at least 0.1 part by weight.

The resist composition comprises the polymer as base resin, an organicsolvent, and an acid generator (i.e., compound capable of generating anacid in response to high-energy radiation), and optionally, adissolution regulator, basic compound, surfactant, acetylene alcohol,and other components.

Specifically, the resist composition contains an acid generator suchthat it may function as a chemically amplified resist composition. Theacid generator is typically a compound capable of generating an acid inresponse to actinic light or radiation, known as photoacid generator(PAG). An appropriate amount of the PAG used is 0.5 to 30 parts, morepreferably 1 to 20 parts by weight per 100 parts by weight of the baseresin. The PAG is any compound capable of generating an acid uponexposure to high-energy radiation. Suitable PAGs include sulfoniumsalts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, andoxime-O-sulfonate acid generators. The acid generators may be used aloneor in admixture of two or more. Exemplary of the acid generated by PAGare sulfonic acids, imidic acids and methide acids. Of these, sulfonicacids which are fluorinated at α-position are most commonly used. Wherethe acid labile group is an acetal group susceptible to deprotection,fluorination at α-position is not always necessary. Where the basepolymer has recurring units of acid generator copolymerized therein, theacid generator need not be separately added.

Examples of the organic solvent used herein are described in JP-A2008-111103, paragraphs [0144] to [0145] (U.S. Pat. No. 7,537,880).Specifically, exemplary solvents include ketones such as cyclohexanoneand methyl-2-n-amyl ketone; alcohols such as 3-methoxybutanol,3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether,ethylene glycol monomethyl ether, propylene glycol monoethyl ether,ethylene glycol monoethyl ether, propylene glycol dimethyl ether, anddiethylene glycol dimethyl ether; esters such as propylene glycolmonomethyl ether acetate (PGMEA), propylene glycol monoethyl etheracetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate,tert-butyl propionate, and propylene glycol mono-tert-butyl etheracetate; and lactones such as y-butyrolactone, and mixtures thereof.Where an acid labile group of acetal form is used, a high-boilingalcohol solvent such as diethylene glycol, propylene glycol, glycerol,1,4-butanediol or 1,3-butanediol may be added for acceleratingdeprotection reaction of acetal.

Exemplary basic compounds include primary, secondary and tertiary aminecompounds, specifically amine compounds having a hydroxyl, ether, ester,lactone, cyano or sulfonate group, as described in JP-A 2008-111103,paragraphs [0146] to [0164], and compounds having a carbamate group, asdescribed in JP 3790649. Also, onium salts such as sulfonium salts,iodonium salts and ammonium salts of sulfonic acids which are notfluorinated at α-position as described in US 2008153030 (JP-A2008-158339) and similar onium salts of carboxylic acid as described inJP 3991462 and JP 426803 may be used as the quencher. They may also beadded to the shrink agent.

Where the acid labile group is an acetal group which is very sensitiveto acid, the acid for eliminating the protective group need notnecessarily be a sulfonic acid which is fluorinated at α-position,imidic acid or methide acid. Even with a sulfonic acid which is notfluorinated at a-position, deprotection reaction may take place in somecases. Since an onium salt of sulfonic acid cannot be used as thequencher in this event, an onium salt of imidic acid is preferably usedalone.

Exemplary surfactants are described in JP-A 2008-111103, paragraphs[0165]-[0166]. Exemplary dissolution regulators are described in JP-A2008-122932 (US 2008090172), paragraphs [0155]-[0178], and exemplaryacetylene alcohols in paragraphs [0179]-[0182].

Also a polymeric additive may be added for improving the waterrepellency on surface of a resist film as spin coated. This additive maybe used in the topcoatless immersion lithography. These additives have aspecific structure with a 1,1,1,3,3,3-hexafluoro-2-propanol residue andare described in JP-A 2007-297590 and JP-A 2008-111103. The waterrepellency improver to be added to the resist composition should besoluble in the organic solvent as the developer. The water repellencyimprover of specific structure with a 1,1,1,3,3,3-hexafluoro-2-propanolresidue is well soluble in the developer. A polymer having an aminogroup or amine salt copolymerized as recurring units may serve as thewater repellent additive and is effective for preventing evaporation ofacid during PEB and avoiding any hole pattern opening failure afterdevelopment. An appropriate amount of the water repellency improver is0.1 to 20 parts, preferably 0.5 to 10 parts by weight per 100 parts byweight of the base resin.

Notably, an appropriate amount of the organic solvent is 100 to 10,000parts, preferably 300 to 8,000 parts by weight, and an appropriateamount of the basic compound is 0.0001 to 30 parts, preferably 0.001 to20 parts by weight, per 100 parts by weight of the base resin. Thedissolution regulator, surfactant and acetylene alcohol may be used inany suitable amounts, depending on their purpose of addition.

Referring to FIGS. 1 and 2, the pattern shrinking process of theinvention is described. First, as shown in FIG. 1 (A), a chemicallyamplified resist composition is applied onto a processable substrate 20on a substrate 10 to form a photoresist film 30 thereon. If necessary, ahard mask layer (not shown) may intervene between the resist film 30 andthe processable substrate 20. By standard techniques, the resist film 30is subjected to exposure (FIG. 1 (B)), PEB, and organic solventdevelopment to form a negative resist pattern 30 a (FIG. 1 (C)). Ashrink agent 40 is applied onto the negative resist pattern 30 a tocover the pattern as shown in FIG. 2 (D). The shrink agent coating isbaked, during which the heat functions to evaporate off the solvent andto cause the acid to diffuse into the shrink agent coating 40. With theacid, the polymer in the shrink agent coating undergoes deprotectionreaction. Thereafter, a solvent is applied to remove the excessiveshrink agent 40, leaving a shrink agent film 40 a over the resistpattern 30 a. This means that the resist pattern 30 a is thickened at50, that is, the width of spaces in the resist pattern is shrunk asshown in FIG. 2 (E). Using the shrunk pattern 50 as a mask, theprocessable substrate 20 is dry etched as shown in FIG. 2 (F).

The substrate 10 used herein is generally a silicon substrate. Theprocessable substrate (or target film) 20 used herein includes SiO₂,SiN, SiON, SiOC, p-Si, α-Si, TiN, WSi, BPSG, SOG, Cr, CrO, CrON, MoSi,low dielectric film, and etch stopper film. The hard mask may be ofSiO₂, SiN, SiON or p-Si. Sometimes, an undercoat in the form of carbonfilm or a silicon-containing intermediate film may be laid instead ofthe hard mask, and an organic antireflective coating may be interposedbetween the hard mask and the resist film.

While a resist film (30) of a chemically amplified resist composition isformed on a processable substrate (20) on a substrate (10) directly orvia an intermediate intervening layer as mentioned above, the resistfilm preferably has a thickness of 10 to 1,000 nm and more preferably 20to 500 nm. Prior to exposure, the resist film is heated or prebaked,preferably at a temperature of 50 to 180° C., especially 60 to 150° C.for a time of 10 to 300 seconds, especially 15 to 200 seconds.

Next the resist film is exposed. For the exposure, preference is givento high-energy radiation, which is typically i-line of wavelength 364nm, KrF excimer laser of wavelength 248 nm, ArF excimer laser ofwavelength 193 nm, EUV of wavelength 13.5 nm, or electron beam (EB). Theexposure may be done either in a dry atmosphere such as air or nitrogenstream or by immersion lithography in water. The ArF immersionlithography uses deionized water or liquids having a refractive index ofat least 1 and highly transparent to the exposure wavelength such asalkanes as the immersion solvent. In the immersion lithography, theprebaked resist film is exposed to light through a projection lens, withpure water or another liquid introduced between the resist film and theprojection lens. Since this allows lenses to be designed to a NA of 1.0or higher, formation of finer feature size patterns is possible. Theimmersion lithography is important for the ArF lithography to survive tothe 45-nm node. In the case of immersion lithography, deionized waterrinsing (or post-soaking) may be carried out after exposure for removingwater droplets left on the resist film, or a protective film may beapplied onto the resist film after pre-baking for preventing anyleach-out from the resist film and improving water slip on the filmsurface. The resist protective film used in the immersion lithography ispreferably formed from a solution of a polymer having1,1,1,3,3,3-hexafluoro-2-propanol residues which is insoluble in water,but soluble in an alkaline developer liquid, in a solvent selected fromalcohols of 4 to 10 carbon atoms, ethers of 8 to 12 carbon atoms, andmixtures thereof. After formation of the photoresist film, deionizedwater rinsing (or post-soaking) may be carried out for extracting theacid generator and the like from the film surface or washing awayparticles, or after exposure, rinsing (or post-soaking) may be carriedout for removing water droplets left on the resist film.

Exposure is preferably performed in an exposure dose of about 1 to 200mJ/cm², more preferably about 10 to 100 mJ/cm². This is followed bybaking (PEB) on a hot plate at 50 to 150° C. for 1 to 5 minutes,preferably at 60 to 120° C. for 1 to 3 minutes.

Thereafter the exposed resist film is developed with a developerconsisting of an organic solvent for 0.1 to 3 minutes, preferably 0.5 to2 minutes by any conventional techniques such as dip, puddle and spraytechniques. In this way, a negative resist pattern is formed on thesubstrate. The organic solvent used as developer is preferably selectedfrom among 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone,4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone,methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate,butyl acetate, isobutyl acetate, amyl acetate, butenyl acetate, isoamylacetate, propyl formate, butyl formate, isobutyl formate, amyl formate,isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate,ethyl crotonate, methyl benzoate, ethyl benzoate, phenyl acetate, benzylacetate, methyl phenylacetate, benzyl formate, phenylethyl formate,methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, and2-phenylethyl acetate, and mixtures thereof.

At the end of development, the resist film may be rinsed. As the rinsingliquid, a solvent which is miscible with the developer and does notdissolve the resist film is preferred. Suitable solvents includealcohols of 3 to 10 carbon atoms, ether compounds of 8 to 12 carbonatoms, alkanes, alkenes, and alkynes of 6 to 12 carbon atoms, andaromatic solvents. Specifically, suitable alkanes of 6 to 12 carbonatoms include hexane, heptane, octane, nonane, decane, undecane,dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane,methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, andcyclononane. Suitable alkenes of 6 to 12 carbon atoms include hexene,heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene,cycloheptene, and cyclooctene. Suitable alkynes of 6 to 12 carbon atomsinclude hexyne, heptyne, and octyne. Suitable alcohols of 3 to 10 carbonatoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol,2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol,2-pentanol, 3-pentanol, tert-amyl alcohol, neopentyl alcohol,2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol,cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol,3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol,2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol,3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol,4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol,cyclohexanol, and 1-octanol. Suitable ether compounds of 8 to 12 carbonatoms include di-n-butyl ether, diisobutyl ether, di-sec-butyl ether,di-n-pentyl ether, diisopentyl ether, di-sec-pentyl ether, di-tert-amylether, and di-n-hexyl ether. Suitable aromatic solvents include toluene,xylene, ethylbenzene, isopropylbenzene, t-butylbenzene, and mesitylene.The solvents may be used alone or in admixture. After the rinse liquidis applied, the substrate may be dried by spin drying and bake. However,rinsing is not essential. As long as the step of spin drying thesubstrate after the developer is applied thereto is included, therinsing step may be omitted.

Following the development, the shrink agent of the invention is appliedonto the resist pattern to form a shrink agent coating, preferablyhaving a thickness of 1 to 100 nm, more preferably 1.5 to 50 nm. Theshrink agent coating is baked at a temperature of 40 to 150° C. for 5 to300 seconds. Bake functions to evaporate off the solvent and to induceacid diffusion from the resist film to the shrink agent and deprotectionreaction to generate carboxyl and/or hydroxyl groups in the shrink agentcoating, for thereby rendering the shrink agent coating insoluble in theorganic solvent developer due to a polarity change by the generatedcarboxyl and/or hydroxyl groups.

Finally, the excessive shrink agent is removed, preferably using theorganic solvent developer. This means that development of the resistfilm and removal of the shrink agent can be performed with an identicalorganic solvent. The nozzle needed is only one.

EXAMPLE

Examples of the invention are given below by way of illustration and notby way of limitation. The abbreviation “pbw” is parts by weight, andPGMEA is propylene glycol monomethyl ether acetate. For all polymers, Mwand Mn are determined by GPC versus polystyrene standards.

Synthesis Example

Polymers (for use in shrink agent and resist composition) weresynthesized by combining suitable monomers in tetrahydrofuran solvent,effecting copolymerization reaction, crystallizing from methanol,repeatedly washing with hexane, isolation and drying. There wereobtained random copolymers, designated Polymers 1 to 15, ComparativePolymers 1, 2, Resist Polymer 1, and Water-repellent Polymer 1. Thepolymers were analyzed for composition by ¹H-NMR spectroscopy and for Mwand Mw/Mn by GPC. The polymers are identified below with theiranalytical data.

Examples 1 to 39 and Comparative Examples 1 to 4

A shrink agent solution was prepared by mixing the polymer synthesizedabove (Polymers 1 to 15 or Comparative Polymers 1, 2), additive (e.g.,sulfonium salt), and solvent in accordance with the formulation ofTables 1 and 2, and filtering through a Teflon® filter having a poresize of 0.2 μm. Components shown in Tables 1 and 2 are identified below.

Acid Generator: PAG1 of the Following Structural Formula

Sulfonium Salts 1 to 12, Iodonium Salt 1, Ammonium Salts 1, 2 and AmineQuenchers 1, 2 of the Following Structural Formulae

TABLE 1 Polymer Additive Organic solvent Shrink agent (pbw) (pbw) (pbw)Shrink agent 1 Polymer — isoamyl acetate(6,000) 1 (100) Shrink agent 2Polymer Sulfonium isoamyl acetate(6,000) 2 (100) salt 1 (2.0) Shrinkagent 3 Polymer Sulfonium isoamyl acetate(6,000) 3 (100) salt 1 (2.0)Shrink agent 4 Polymer Sulfonium isoamyl acetate(6,000) 4 (100) salt 1(2.0) Shrink agent 5 Polymer Sulfonium isoamyl acetate(6,000) 5 (100)salt 1 (2.0) Shrink agent 6 Polymer Sulfonium isoamyl acetate(6,000) 6(100) salt 1 (2.0) Shrink agent 7 Polymer Sulfonium isoamylacetate(6,000) 7 (100) salt 1 (2.0) Shrink agent 8 Polymer Sulfoniumisoamyl acetate(6,000) 8 (100) salt 1 (2.0) Shrink agent 9 PolymerSulfonium isoamyl acetate(6,000) 9 (100) salt 1 (2.0) Shrink agent 10Polymer Sulfonium isoamyl acetate(6,000) 10 (100) salt 1 (2.0) Shrinkagent 11 Polymer Sulfonium isoamyl acetate(6,000) 11 (100) salt 1 (2.0)Shrink agent 12 Polymer Sulfonium isoamyl acetate(6,000) 12 (100) salt 1(2.0) Shrink agent 13 Polymer Sulfonium isoamyl acetate(6,000) 13 (100)salt 1 (2.0) Shrink agent 14 Polymer Sulfonium isoamyl acetate(6,000) 2(100) salt 2 (2.0) Shrink agent 15 Polymer Sulfonium isoamylacetate(6,000) 2 (100) salt 3 (2.0) Shrink agent 16 Polymer Sulfoniumisoamyl acetate(6,000) 2 (100) salt 4 (2.0) Shrink agent 17 PolymerSulfonium isoamyl acetate(6,000) 2 (100) salt 5 (2.0) Shrink agent 18Polymer Sulfonium isoamyl acetate(6,000) 2 (100) salt 6 (2.0) Shrinkagent 19 Polymer Sulfonium isoamyl acetate(6,000) 2 (100) salt 7 (2.0)Shrink agent 20 Polymer Sulfonium isoamyl acetate(6,000) 2 (100) salt 8(2.0) Shrink agent 21 Polymer Amine isoamyl acetate(6,000) 2 (100)quencher 1 (0.5)

TABLE 2 Polymer Additive Organic solvent Shrink agent (pbw) (pbw) (pbw)Shrink agent 22 Polymer Sulfonium isoamyl acetate(600) 2 (100) salt 9(2.0) Shrink agent 23 Polymer Sulfonium isoamyl acetate(600) 2 (100)salt 10 (2.0) Shrink agent 24 Polymer Sulfonium isoamyl acetate(600) 2(100) salt 11 (2.0) Shrink agent 25 Polymer Sulfonium isoamylacetate(600) 2 (100) salt 12 (2.0) Shrink agent 26 Polymer Iodoniumisoamyl acetate(600) 2 (100) salt 1 (2.0) Shrink agent 27 PolymerAmmonium isoamyl acetate(600) 2 (100) salt 1 (1.5) Shrink agent 28Polymer Sulfonium ethyl 2 (100) salt 1 (2.0) 2-methylvalerate(600)Shrink agent 29 Polymer Sulfonium 2-methylbutyl 2 (100) salt 1 (2.0)acetate(600) Shrink agent 30 Polymer Sulfonium n-amyl acetate(600) 2(100) salt 1 (2.0) Shrink agent 31 Polymer Sulfonium n-hexylacetate(400) 2 (100) salt 1 (2.0) 2-nonane(200) Shrink agent 32 PolymerSulfonium 3-methylbutyl 2 (100) salt 1 (2.0) butyrate(500) anisole(100)Shrink agent 33 Polymer Sulfonium ethyl hexanoate(500) 2 (100) salt 1(2.0) diisoamyl ether(100) Shrink agent 34 Polymer Sulfonium ethyl 2(100) salt 1 (2.0) 2-methylbutyrate(400) isoamyl isobutyrate(200) Shrinkagent 35 Polymer Amine allyl hexanoate(300) 2 (100) quencher ethyl 1(0.5) 2-methylbutyrate(300) Shrink agent 36 Polymer Amine allylhexanoate(300) 2 (100) quencher ethyl 2 (0.5) 2-methylbutyrate(300)Shrink agent 37 Polymer Ammonium isoamyl acetate(600) 14 (100) salt 1(1.5) Shrink agent 38 Polymer Ammonium isoamyl acetate(600) 14 (100)salt 2 (3.5) Shrink agent 39 Polymer Ammonium isoamyl acetate(600) 15(100) salt 2 (3.5) Comparative Comparative Sulfonium isoamylacetate(600) shrink agent 1 Polymer salt 1 (2.0) 1 (100) ComparativeComparative Sulfonium isoamyl acetate(600) shrink agent 2 Polymer salt 1(2.0) 2 (100) Comparative Polymer Sulfonium PGMEA(3,000) shrink agent 31 (100) salt 1 (2.0) Comparative Polymer Sulfonium butyl acetate(3,000)shrink agent 4 1 (100) salt 1 (2.0)

Preparation of Resist Composition

A resist composition in solution form was prepared by dissolving apolymer (Resist Polymer 1), acid generator, quencher, andwater-repellent polymer in a solvent in accordance with the formulationof Table 3, and filtering through a filter with a pore size of 0.2 μm.The solvent contained 100 ppm of surfactant FC-4430 (3M-Sumitomo Co.,Ltd.).

TABLE 3 Acid Water Organic Polymer generator Quencher repellent solventResist (pbw) (pbw) (pbw) (pbw) (pbw) Resist Resist PAG1 Amine Water-PGMEA(2500) 1 Polymer (10.0) quencher repellent γ-butyrolac- 1 (100) 1(2.0) Polymer 1 tone(200) (3.0)

ArF Lithography Patterning Test

On a silicon wafer, a spin-on carbon film ODL-102 (Shin-Etsu ChemicalCo., Ltd.) was deposited to a thickness of 200 nm and asilicon-containing spin-on hard mask SHB-A940 was deposited thereon to athickness of 35 nm. On this substrate for trilayer process, the resistcomposition in Table 3 was spin coated, then baked on a hot plate at100° C. for 60 seconds to form a resist film of 100 nm thick. Using anArF excimer laser immersion lithography scanner NSR-610C (Nikon Corp.,NA 1.30, c 0.98/0.78, dipole opening 20 deg., azimuthally polarizedillumination), the resist film was exposed through a 6% halftone phaseshift mask while varying the exposure dose. After the exposure, theresist film was baked (PEB) at 90° C. for 60 seconds and puddledeveloped in n-butyl acetate for 30 seconds to form a trench patternhaving a space width of 45 nm and a pitch of 100 nm.

The shrink agent shown in Tables 1 and 2 was applied onto the resistpattern after development to cover the pattern. The shrink agent coatingwas baked at the temperature shown in Tables 4 and 5 for 60 seconds.This was followed by puddle development in n-butyl acetate for 20seconds to remove the shrink agent. Both after development and aftershrink treatment, the pattern was observed under a CD-SEM (CG-4000 byHitachi, Ltd.) to measure the size of trenches at a pitch of 100 nm andedge roughness. The results are shown in Tables 4 and 5.

TABLE 4 Pattern Pattern size after LER after size after LER after Bakeremoval of removal of development development temp. shrink agent shrinkagent Resist (nm) (3σ, nm) Shrink agent (° C.) (nm) (3σ, nm) Example 1Resist 1 (100) 45 2.7 Shrink agent 1 130 29 3.1 2 Resist 1 (100) 46 2.6Shrink agent 2 135 32 2.1 3 Resist 1 (100) 45 2.7 Shrink agent 3 130 282.8 4 Resist 1 (100) 45 2.7 Shrink agent 4 130 30 2.7 5 Resist 1 (100)45 2.7 Shrink agent 5 135 33 2.5 6 Resist 1 (100) 45 2.7 Shrink agent 6130 30 2.4 7 Resist 1 (100) 45 2.7 Shrink agent 7 130 31 2.6 8 Resist 1(100) 45 2.7 Shrink agent 8 130 35 2.6 9 Resist 1 (100) 45 2.7 Shrinkagent 9 135 31 2.5 10 Resist 1 (100) 45 2.5 Shrink agent 10 125 35 2.511 Resist 1 (100) 45 2.7 Shrink agent 11 130 31 2.6 12 Resist 1 (100) 452.7 Shrink agent 12 120 29 1.9 13 Resist 1 (100) 45 2.7 Shrink agent 13135 31 2.3 14 Resist 1 (100) 45 2.7 Shrink agent 14 135 32 2.5 15 Resist1 (100) 45 2.7 Shrink agent 15 135 34 2.6 16 Resist 1 (100) 45 2.7Shrink agent 16 135 34 2.5 17 Resist 1 (100) 45 2.7 Shrink agent 17 14034 2.6 18 Resist 1 (100) 45 2.7 Shrink agent 18 135 30 2.8 19 Resist 1(100) 45 2.7 Shrink agent 19 135 31 2.4 20 Resist 1 (100) 45 2.7 Shrinkagent 20 135 33 2.3 21 Resist 1 (100) 45 2.7 Shrink agent 21 135 34 2.2

TABLE 5 Pattern Pattern size after LER after size after LER after Bakeremoval of removal of development development temp. shrink agent shrinkagent Resist (nm) (3σ, nm) Shrink agent (° C.) (nm) (3σ, nm) Example 22Resist 1 (100) 45 2.7 Shrink agent 22 135 29 2.3 23 Resist 1 (100) 463.3 Shrink agent 23 135 32 2.1 24 Resist 1 (100) 45 2.7 Shrink agent 24135 28 2.7 25 Resist 1 (100) 45 2.7 Shrink agent 25 135 32 2.7 26 Resist1 (100) 45 2.7 Shrink agent 26 135 33 2.5 27 Resist 1 (100) 45 2.7Shrink agent 27 135 31 2.4 28 Resist 1 (100) 45 2.7 Shrink agent 28 13534 2.6 29 Resist 1 (100) 45 2.7 Shrink agent 29 135 35 2.6 30 Resist 1(100) 45 2.7 Shrink agent 30 135 33 2.5 31 Resist 1 (100) 45 2.7 Shrinkagent 31 135 35 2.5 32 Resist 1 (100) 45 2.7 Shrink agent 32 135 33 2.633 Resist 1 (100) 45 2.7 Shrink agent 33 135 29 2.3 34 Resist 1 (100) 452.7 Shrink agent 34 135 31 2.3 35 Resist 1 (100) 45 2.7 Shrink agent 35135 32 2.5 36 Resist 1 (100) 45 2.7 Shrink agent 36 135 34 2.6 37 Resist1 (100) 45 2.7 Shrink agent 37 120 34 2.4 38 Resist 1 (100) 45 2.7Shrink agent 38 120 31 2.6 39 Resist 1 (100) 45 2.7 Shrink agent 39 13527 2.1 Compar- 1 Resist 1 (100) 45 2.7 Comparative 120 47 3.1 ativeshrink agent 1 Example 2 Resist 1 (100) 45 2.7 Comparative 110 49 3.1shrink agent 2 3 Resist 1 (100) 45 2.7 Comparative 110 pattern — shrinkagent 3 vanished 4 Resist 1 (100) 45 2.7 Comparative 110 42 4.5 shrinkagent 4

While the invention has been illustrated and described in typicalembodiments, it is not intended to be limited to the details shown,since various modifications and substitutions can be made withoutdeparting in any way from the spirit of the present invention. As such,further modifications and equivalents of the invention herein disclosedmay occur to persons skilled in the art using no more than routineexperimentation, and all such modifications and equivalents are believedto be within the spirit and scope of the invention as defined by thefollowing claims.

Japanese Patent Application No. 2014-221355 is incorporated herein byreference.

Although some preferred embodiments have been described, manymodifications and variations may be made thereto in light of the aboveteachings. It is therefore to be understood that the invention may bepracticed otherwise than as specifically described without departingfrom the scope of the appended claims.

1. A pattern forming process comprising the steps of: applying a resistcomposition onto a substrate, said resist composition comprising apolymer comprising recurring units having an acid labilegroup-substituted carboxyl group, an acid generator and an organicsolvent, prebaking to form a resist film, exposing the resist film tohigh-energy radiation, baking the film, developing the exposed resistfilm in an organic solvent-based developer to form a negative pattern,applying a shrink agent onto the negative pattern, said shrink agentbeing a solution of a polymer comprising recurring units having an acidlabile group-substituted hydroxyl and/or carboxyl group in a solventselected from the group consisting of ester solvents of 7 to 16 carbonatoms and ketone solvents of 8 to 16 carbon atoms, baking, and removingthe excessive shrink agent with the organic solvent-based developer forthereby shrinking the size of spaces in the pattern.
 2. The patternforming process of claim 1 wherein the polymer in the shrink agentcomprises recurring units having an acid labile group-substitutedhydroxyl and/or carboxyl group, represented by the general formula (1):

wherein R¹ and R³ each are hydrogen or methyl, R² and R⁵ each are anacid labile group, X₁ is a single bond, a phenylene or naphthylenegroup, or —C(═O)—O—R⁶—, R⁶ is a straight, branched or cyclic C₁-C₁₀alkylene group which may contain ether, ester, lactone ring or hydroxyl,or a phenylene or naphthylene group, X₂ is a single bond, a phenylene ornaphthylene group which may contain nitro, cyano or halogen, or—C(═O)—O—R⁷—, —C(═O)—NH—R⁷—, —O—R⁷—, or —S—R⁷—, R⁷ is a straight,branched or cyclic C₁-C₁₀ alkylene group which may contain ether, ester,lactone ring or hydroxyl, or a phenylene or naphthylene group which maycontain a straight, branched or cyclic C₁-C₆ alkyl, alkoxy, acyl,acyloxy, C₂-C₆ alkenyl, alkoxycarbonyl, C₆-C₁₀ aryl, nitro, cyano, orhalogen, R⁴ is a single bond, a di to penta-valent, straight, branchedor cyclic C₁-C₁₆ aliphatic hydrocarbon group, or phenylene group, whichmay contain ether or ester, 0≦a1≦1.0, 0≦a2<1.0, 0<a1+a2≦1.0, and n is 1to
 4. 3. The pattern forming process of claim 2 wherein the polymercomprising recurring units having an acid labile group-substitutedhydroxyl and/or carboxyl group, represented by formula (1) furthercomprises recurring units (b) having a hydroxyl, carboxyl, lactone ring,lactam ring, sultone ring, sulfone, sulfonic acid ester, sulfonamide,carboxylic acid amide, nitro, cyano, thienyl, furyl, pyrrole, acidanhydride, imide, —NH—(C═O)—O—, —S—(C═O)—O—, or —ON(═O₂)—, recurringunits (d) having an oxirane or oxetane ring, and/or recurring units (e)having an amino group.
 4. The pattern forming process of claim 1 whereinthe solvent in the shrink agent is at least one solvent selected fromthe group consisting of ester solvents of 7 to 16 carbon atoms includingamyl acetate, isoamyl acetate, 2-methylbutyl acetate, hexyl acetate,2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate,hexyl formate, ethyl valerate, propyl valerate, isopropyl valerate,butyl valerate, isobutyl valerate, tert-butyl valerate, amyl valerate,isoamyl valerate, ethyl isovalerate, propyl isovalerate, isopropylisovalerate, butyl isovalerate, isobutyl isovalerate, tert-butylisovalerate, isoamyl isovalerate, ethyl 2-methylvalerate, butyl2-methylvalerate, ethyl pivalate, propyl pivalate, isopropyl pivalate,butyl pivalate, tert-butyl pivalate, ethyl pentenoate, propylpentenoate, isopropyl pentenoate, butyl pentenoate, tert-butylpentenoate, propyl crotonate, isopropyl crotonate, butyl crotonate,tert-butyl crotonate, butyl propionate, isobutyl propionate, tert-butylpropionate, benzyl propionate, ethyl hexanoate, allyl hexanoate, propylbutyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate,tert-butyl butyrate, ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate,methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenylacetate, benzyl acetate, methyl phenylacetate, benzyl formate,phenylethyl formate, methyl 3-phenylpropionate, ethyl phenylacetate, and2-phenylethyl acetate, and ketone solvents of 8 to 16 carbon atomsincluding 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone,4-nonanone, 5-nonanone, ethylcyclohexanone, ethylacetophenone, ethyln-butyl ketone, di-n-butyl ketone, and diisobutyl ketone.
 5. The patternforming process of claim 1 wherein the shrink agent further comprises asalt compound having the general formula (3)-1 or (3)-2:R¹¹—CO₂ ⁻M⁺  (3)-1R¹²—SO₃ ⁻M⁺  (3)-2 wherein R¹¹ and R¹² each are a straight, branched orcyclic C₁-C₂₀ alkyl group, C₂-C₂₀ alkenyl group or C₆-C₂₀ aryl groupwhich may contain fluorine, ether, ester, lactone ring, lactam ring,carbonyl or hydroxyl, and M is sulfonium, iodonium or ammonium.
 6. Thepattern forming process of claim 1 wherein the polymer in the resistcomposition comprises recurring units (a3) having the general formula(2):

wherein R⁸ is hydrogen or methyl, R⁹ is an acid labile group, Z is asingle bond or —C(═O)—O—R¹⁰—, R¹⁰ is a straight, branched or cyclicC₁-C₁₀ alkylene group which may contain ether or ester, or naphthylenegroup, and 0<a3<1.0.
 7. The pattern forming process of claim 1 whereinthe developer comprises at least one organic solvent selected from thegroup consisting of 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone,4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone,methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate,butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, butenylacetate, propyl formate, butyl formate, isobutyl formate, amyl formate,isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate,ethyl crotonate, methyl propionate, ethyl propionate, ethyl3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyllactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethylbenzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzylformate, phenylethyl formate, methyl 3-phenylpropionate, benzylpropionate, ethyl phenylacetate, and 2-phenylethyl acetate.
 8. Thepattern forming process of claim 1 wherein the high-energy radiation inthe exposure step is i-line of wavelength 364 nm, KrF excimer laser ofwavelength 248 nm, ArF excimer laser of wavelength 193 nm, EUV ofwavelength 13.5 nm, or EB.
 9. A shrink agent comprising a polymercomprising recurring units having an acid labile group-substitutedhydroxyl and/or carboxyl group, an ester solvent of 7 to 16 carbon atomsand/or ketone solvent of 8 to 16 carbon atoms, and a salt compoundhaving the general formula (3)-1 or (3)-2:R¹¹—CO₂ ⁻M⁺  (3)-1R¹²—SO₃ ⁻M⁺  (3)-2 wherein R¹¹ and R¹² each are a straight, branched orcyclic C₁-C₂₀ alkyl group, C₂-C₂₀ alkenyl group or C₆-C₂, aryl groupwhich may contain fluorine, ether, ester, lactone ring, lactam ring,carbonyl or hydroxyl, and M is sulfonium, iodonium or ammonium.